Indigoid vat dyestuffs



Patented May 18, 1937 UNITED STATES PATENT emcememoir) VAT DYEsirUFrs Jim-Sim; Froehlilch, Basel, Switierland, assignor to the arm Society of Chemical Industry-In Basle, Basel, Switzerland v 7 No Drawi ng. Application :11; 1936,

Serial No. 115,446. In switiilafia neiililbel" Claims. (01. 230-53) This invention relates to the manufacture of new indigoid vat dyestuffs by either oxidizing hydroxythionaphthenes and indoxyls containing at least one alkoxy-alkoxy -g roup, orby condensing them or their reactive Z-derivatives with components suitable for making indigoid dyestuffs, and if desired halogenating the dyestuffs thus produced,

The hydroxythionaphthenes and indoxyls or their reactive 2-derivatives used as parent materials may be made by the usual general methods, for example from amines and sulfonic acids which contain at least one alkoxy-alkoxy-group,

CHaO-"CHa-CHr-O densation of the hydroxythionaphthenes and in doxyls as such or in the form of their reactive 2- clerivatives, for instance the 2-anil or 2-keto compounds, in solution or in suspension, for instance in concentrated sulfuric acid, in benzene, in chlorobenzene or in tetrachlorethane with indigoid components, for instance l-hydroxynaphthalenes (or a halogen derivative, for instance 4-chloroor 4-bromo-1-hydroxynaphthalenes, or an alkoxy derivative, for instance 4'- ethoxyand l methoxy 1 -hydroxynaphthalenes), hydroxyanthracenes, or five-membered condensed ring systems, for example isatins, naphthisatins indoxyls, thionaphthenequinoiies, hydroxythionaphthenes and acenaphthenequinones. In such a manner there are obtained both symmetrical and unsymmetrical indigoid dyestuffs. I

The new indigoid dyestuffs may be treated with halogenating agents; they may also be converted into their luco ester salts. They may be usedfor dyeing and printing vegetable, animal and arti ficial fibers, for instance cotton, wool and-acetate artificial silk, or as pigments; In comparison with the known indigoid dyestuffs they are distinguished by their free solubility in organic solvents; such as chlorobenzene, a property which fits them for use in coloring masses and lacquers of various kinds and origin. vi

The following examples illustrate the invention; the parts being by weight:--

Example 1 224 parts of dmethoxy-ethoxy-3 liydroxythiog-i naphthene are dissolved with aid of heat in 1000 parts of caustic sodaisolution of 12 per cent. strength with the addition of some alcohol; this solution is mixed while gently boiling with the quantity of. a ground aqueous suspension of sul: fur calculated as necessary for the oxidation and added in portions. After a short boiling the formation of dyestufi is complete. The mass is filtered and. the dyestuif of the formula CO CO washed and dried. T It is a violet powder soluble in concentrated sulfuric acid to a' yellow-green solution. It dissolves surprisingly freely in hot chlorobenzene and crystallizes therefrom in the formpf violet needles of melting point 221 C. The dyestuif forms a yellow vat which dyes cot: ton reddish tints, v

a 'f' in this exa ple instead or 5-m'ethoxy-j e'thoxy-3-hydroxythionaphthene there is used the same proportion of e-memexy-emoxygs: hydroxythionaphthene there is obtained a dyestuff of the formula which dissolves in sulfuric acid to a vicletsolution. It crystallizes from cmerobenzene in the form of orange" needles" of melting point 267 268 C. It" dyes cotton in a; yellow vat" orange may be made as follows: 4-nltro-1-phen0l is converted into l-methoxy-ethoxy-4-nitrobenzene by treatment with'the toluene sulfonic acid ester of glycol-mono-methyl ether. This product is reduced by means of iron in presence of glacial acetic acid in an aqueous alcoholic solution to produce 1-methoxy-ethoxy-4-aminobenzene from which by diazotization, reaction with potassium xanthate, saponification and condensation with chloracetic' acid the l-methoxy-ethoxyphenyl-4-thioglycolic acid of melting point 59C. is obtained. From this thioglycolic acid there is produced by treatment with phosphorus trichloride and aluminum chloride the 5-methoxyethoxy-3 -hydroxy-thionaphthene which distils under 4 mm. pressure at 190C.

The 6 methoxy-ethoxy 3 hydroxythionaphthene may be made as follows:-4-methoxyethoxy-l-aminobenzene hydrochloride is treated by the Herz method with sulfur chloride at 30- C. The 4-methoxy-ethoxy-l:2-phenylenethiazothionium chloride thus obtained is saponified by introduction into aqueous alkali and is condensed which chloracetic acid whereby the anhydride of 4-methoXy-ethoxy-1-amino-2-phenylthio-glycolic acid is obtained; this crystallizes from water in the form of colorless needles of melting point 134 C. From this thio-glycolic acid the nitrile is obtained by diazotization and reaction with copper cyanide and the nitrile is converted into 6-meth0xy-ethoxy-S-hydroxytlfionaphthene by treatment'with sodium sulfide and then with hydrochloric acid.

Example 2 224 parts of fi-methoxy-ethoxy-3-hydroxythionaphthene and 282 parts of 2- (para-dimethylamino-)anil of 3-hydroxythionaphthene are mixed with 4000 parts of alcohol and preferably with a condensation accelerator, for instance sodium carbonate or ammonia, and the mixture is heated to boiling. When condensation is complete the dyestufi of the formula co co 0:0 cmo-cm-cm-o 174 parts of 4-m'ethoxy-l-hydroxynaphthalene are dissolved in 2000 parts of benzene and there are added at C. a solution of 5-methoxyethoxy-isatin chloride made in the known manner from 221 parts of 5-methoxy-ethoxy-isatin and 250 parts of phosphorus pentachloride in benzene. After stirring for a short time:condensation' is complete. After filtering, washing and drying the dyestuff of the formula is obtained in the form of a black-blue powder soluble in concentrated sulfuric acid to a green solution and in chlorobenzene, benzene or alcohol to a blue solution. Itdyes cotton in a yellow vat blue tints.

If in this example there are substituted for the 4-'-methoxy-l-hydroxynaphthalene 257 parts of 4 6-dimethyl-7-bromo- 3 -hydroxythionaphthene there is obtained a dark violet dyestuif which dissolves in concentrated sulfuric acid to a green solution and dyes cotton violet tints in a yellow vat.

The 5-methoxy-ethoxy-isatin used in this example may be made as follows: l-methoxyethoxyl-aminobenzene is condensed by the Sandmeyer method with hydroxylamine and chloral hydrate. From the l-methoxy-ethoxy- 4-iso-nitroso-acetanilide thus formed there is made by treatment with sulfuric acid of 97 per cent. strength at 80 C. the 5-methoxy-isatin which crystallizes from water in the form of dark red needles of melting point 151 C.

Example 4 224 parts of B-methoxy-ethoxy-3-hydroxy thionaphthene are dissolved in 2000 parts of chlorobenzene and at 70 C. there is added a. solution of the 5:7-dichlorisatin chloride made in the known manner from 216 parts of 5:7-dichlorisatin and 250- parts of-phosphorous pentachloride in chlorobenzene. After stirring for a short time condensation is complete. After filtering, Washing and drying the dyestuif of the formula is obtained in the form of a blue-red powder soluble in concentrated sulfuric acid to a green solution and dyeing cotton in a red-yellow vat Bordeaux red tints. It dissolves freely in hot chlorobenzene and crystallizes therefrom in the form of dark red needles of melting point 257-258 C.

If in this example 305 parts of 5:7-dibromisatin are substituted for the 5:7-dichlorisatin a. dyestuff of similar properties is obtained.

Example 5 a 224 parts of G-methoxy-ethoxy-B-hydroxythionaphthene and 330.5 parts of 2-(para-dimethylamino-.) anil of 5-chloro-7-methyl-3-hydroxythionaphthene are mixed together in 4000 parts of alcohol, preferably with the addition of some sodium carbonate and the mixture is heated to boiling; When condensation is complete the dyestuif of the formula omo-om-om-O is filtered, washed and dried. It is a dark red powder soluble in concentrated sulfuric acid to aviolet-bluesolution. It forms a yellow vat and dyes cottonred tints. .It dyesacetate artificial silk by the usual dyeing operations red-violet. It colors nitrocellulose lacquer strong violet tints.

Earample 6 224 parts of 6methoxy-ethoxy-B hydroXythlonaphthene and 326 parts of 2- (para-dimethylamino-)anil of fi ethoxy-B-hydroXythionaphthene are together mixed in 4000 parts of alcohol and the mixture is heated to boiling. When condensation is complete the dyestuif. of the formula is filtered, washed and dried. It is an orange powder soluble in concentrated sulfuric acid to a pure violet-blue. It crystallizes from chlorobenzene in the form of orange needles of melting point 274 C. and dyes cotton in a yellow vat orange tints. It dyes wool strong orange tints fast to milling.

CHzO-CHr-CHr-O O C2Ha Example 7 /C O C O\ red tints. From chlorobenzene it crystallizes in the form of red needles of melting point 260 C.

The 2-(para-dimethylaminodanil of B-methoxy-ethoxy-B-hydrQXythiOnaphthene is" made by action of para-nitroso-dimethyl-aniline hydrochloride on 6metlioxy-ethox"y-3-ihydroxythionaphthene.

Example 8 174 parts of 4-methoxy-lehydroxynaphthalene are dissolved in 6000 parts of chlorobenzene and at 20 C. there is added a solution of -metho'xyethoxy-7-chlorisatin chloride made in known manner from255 parts of fi-methoxy-ethoxy 'lchlo'r'isatin and 250 parts of phosphorous pentachloride in chlorobenzene. After a short stirring at 40? C. the condensation is complete. When filtered, washed and dried the dyestuff of the formula 0011a has the form of blue needles soluble in concentrated sulfuric acid to a green solution. It crystallizes from chlorobenzene in the form of green-blue needles of melting point 256 C. When printed on cottonv it yields a pure very fast blue-green. i a

The 5-methoxy-7 -chlorisatin is made by treating 5-methoxy-ethoX'y-isatin with sulfuryl chloride at 60-70 C. in glacial acetic acid. It crystallizes from dilute. alcohol in red-orange needles CH3 of melting point 221 C. s S The following table comprises a number of 0 further dyestuffs obtainable by this invention:-

Color of soluggi gg g tioninconc. Color ofvat Dyeingoncotton 5-meigmxy-etlioxy-3-hydroxy-thlonaphthene condensed (1) 2-(parfittllimethylamind) anil of 3-l1ydroxytliio- Red 227-228 Green Yellow Red-violet.

nap ene. (2) 2-(pgra-dlimethylaminm) anil of 2:1-naphth thio-' Brown-violet 267 Violet Yellow Brown.

in oxy. (3) 5:7-dibromisatin chloride Blue 229-230 Green-blue." Red-yellow Blue. (4)5-bromisatmchlor1de Blue Green-bluem. Green-yellow Blue-grey. (5) 2-(para-d1methylamind)amlof5-cl1lor Red-violet... 267 Yell0w-green. Yellow Violet.

S-hydroxytluonaphthene. 2-(para-dimethylamino-) anil of 5-1nethoxy-ethoxy-3-hy- I droxy-thionaphthene condensed with:

(6) 4zizfldimethyl-5:7-dicliloro-3-hydroxythionaph- Violet 264 Green Yellow-orange... Red-violet.

ene. (7) B-hydroxythionaphthene Violet 228 Green Yellow Red-violet. 6-1nehoxy-ethoxy-3-hydroxythionaphthene condensed (8) 2-(paira-dlimethylaminm) anil of 2:1-naphth-thio- Red-brown-. 273 Red-violet-. Red-yellow Red-brown.

in oxy. (9) 5-bromisatin chloride Brewn-vio1et 293 Blue-greed... Red-yellow... Brtown-helioro e. (10) 4-methyl-5-chloro-7-methoxyisatin chloride Brown-violet" Viole f. (ll) 4:5-dichloro-7-methoxy-isatin Violet Violet. (12) 4:7-d1methyl-isat-in qhloride Red-violet." Red-violet (13) 4-chloto-7-methoxy-isatin chlorid r Brewn-violet 244 Blue-green Violet. (14) 2-(para-dunethylamiuo-) anil of (i-amino-li-hy- Red-orange 284 Blue Brown-orange droxythionaphthene.

(l5) 2-(para-dimethylamino-) anil of 6-cl1loro-5- Red-violet- 236 Red-violet..- Red.

methyl;3-hydroxythionaphthene. (l6) 2-$;1l)1are-dmet1hylamino-) anil of 1:2-naphth- Dark brown. 263 Red-violet..- Brown-red.

l0-1Il oxy. 2#(para-dimetliylamino-) anil o! 6-metl1oxy-ethoxy-3- hydroxythionaphtheue condensed with: r

(17) 4:fi-di nethyl-7-bro1i mB-hydroxythionephthene. Red-orange 262 Green Yellow Red. (18) 4:?fi-1dimethyl-5:7-dichloro-3-hydroxy-thionaph- Red-orange Green Yellow Bluish red.

ene. (19) 8-chloro-1z2-naphth-tl1io-indoxyl. Red-brown 271 Violet Yellow Red-brown. 5-metl1oxy-ethoxy-isatin chloride condensed with: v I I (20) 6-n1ethoxy-ethoxy-3-hydroxythionaphthene Blue 251 Red-vlolet- Orange Grey-blue.

' green. (21) 4-chloro-1-hy drow-naphthalene Blue 205 Green-blue. Green-yellow... Grey-blue. (22) 3-hydroxythionaphthene Grey-blue Blue-groom-.. Yellow. Grey-blue.

' is filtered, washed and dried. It is a red powder soluble in concentrated sulfuric acid to a green solution and dyes cotton in a yellow vat fast pure \C= CalIsO-CHr-CHr-O 4 v '00 oo o=o mmo-oxn-om-o Y s V s I oo oo I o=o omlo-onl-onro NH2 7 co co 0:0 CzHsO-OHa-OHg-O -CH3 01 CHI O: NH CHIO-CHIOHP ino-2-phenylthio-glycolic acid.

OCH:

The hitherto unknown compounds which are included in the foregoing table may be made as follows:

2(para-dim,ethylamino-)anil of S-methoxyethoxy-B-hydroxythionaphthene (Dyestufis Nos. 6 and 7) :5-methoxy-ethoxy-3-hydroxythionaphthene is caused to react in aqueous alcoholic solution at 40-50 C. with para-nitroso-dimethylaniline hydrochloride in presence of caustic soda solution.

5-methoxy-ethoxy-V-bromisatin (Dyestuff N0. 27) :5-methoxy-ethoxy-isatin is suspended in glacial acetic acid and treated with bromine at C. The 5-methoxy-ethoxy-7-bromisatin crystallizes from glacial acetic acid in red-brown needles of melting point 215-216 C.

5-ethoxy-ethoxy-isatin (Dyestuffs Nos. 28- 31) 1 ethoxy-ethoxy 4 aminobenzene is caused to react by the Sandmeyer method with hydroxylamine and chloral hydrate and the 1- ethoxy-ethoxy-5-iso-nitroso-acetanilide thus obtained is treated at -100 0. with sulfuric acid. The 5-ethoxy-ethoxy-isatin crystallizes from benzene in small red needles of melting point 101- 102 C.

6 ethoxy ethoxy 3 hydroxythio naphthene (Dyestuffs Nos. 32 and 33): 4-nitro-1-phenol is caused to react with the para-toluene sulfonic acid ester of glycol-mono-ethyl ether. The 1- ethoxy-ethoxy 4 nitrobenzene thus obtained crystallizes from dilute alcohol in yellowish-white needlesof melting point 72 C. By reducing this product'with iron in aqueous alcoholic solution in presence of glacial acetic acid there is obtained 1-ethoxy-ethoxy-4-aminobenzene which boils at I 147 C. under 3mm. pressure. The hydrochloride of the 1-ethoxy-ethoxy-4-aminobenzene is converted by the method of Herz over the ethoxyethoxy-l :2-phenylene-thiazo-tl'1ionium chloride into the anhydride of the 4-ethoxy-ethoxy-1-am- From this there is obtained by scission, diazotization, nitrilation, treatment with sodium'sulfide and hydrochloric acid the 6-ethoxy-ethoxy-3-hydroxythionaphthene which forms needles melting at 84-85 C. v

2(para-dimethylamino-)anil of fi-ethoxyethoxy-3-hydroxythionaphthene (Dyestufi No. 38) :6-ethoxy-ethoxy-3-hydroxythionaphthene is caused to react in aqueous alcoholic solution at 4050 C. with para nitroso dimethylaniline hydrochloride in presence of caustic soda solution; the Z-(para-dimethylamino anil of 6-ethoxy-ethoxy-3-hydroxythionaphthene crystallizes from benzene in needles of melting point 121 C.

4 -methyl-5-chloro '7 methoxy-ethoxy-isatin (Dyestuff No. 39) :l-hydroxy-2-nitro-4-methylbenzene is converted by treatment with the para-toluene sulfonic acid ester of the glycolmono-methyl ether into 1-methoxy-ethoxy-2- nitro--methylbenzene. From this product there is obtained by reduction the l-methoxy-ethoxy- 2-amino-4-methylbenzene which by the method of Sandmeyer is converted over the 1-methoxyethoxy 4 methyl- 2 -iso-nitroso-acetanilide of melting point 133 C. methoxy-ethoxy-isatin. This isatin crystallizes from benzene in red-orange needles of melting point 161 C. The chlorination is carried out in a suspension in glacial acetic acid at YO- C. by means of sulfuryl chloride. The chlorinated 4-methyl-7-methoXy-ethoxy-isatin crystallizes in red laminae of melting point C.

l-methyl-5-bromo-7-methoxy ethoxy isatin (Dyestuffs Nos. 40-42) :-the 4-methyl-7-methoXy-ethoXy-isatin is brominated at the boiling temperature by bromine in a glacial acetic acid suspension; the brominated 4-methyl-7-methoxy-ethoXy-isatin crystallizes from chlorobenzene in red needles of melting point C.

l-methoxy-ethoxy-S-bromo 7 methyl-isatin (Dyestufi N0. 43) :1-hydroxy-3-nitro-4-methylbenzene is converted by treatment with the paratoluene sulfonic acid ester of glycol-mono-methyl ether into 1-methoxy-3-nitro4-methylbenzene of melting point 54 C. From this product there is obtained by reduction the 1-methoxy-ethoxy-3- aminol-methylbenzene which boils under 9 mm. pressure at 172 C. This may be converted by the Sandmeyer method by action of hydroxylamine and chloral hydrate into the 1-methoxyinto the 4-methyl-7- wherein R represents a benzene nucleus substituted by at least one alkoxy-alkoxy group and R1 represents the radical of an indigoid component.

3. Indigoid vat dyestuffs of the general formula wherein R represents a benzene nucleus substituted by at least one alkoxy-alkoxy group and R2 represents a benzene nucleus.

4. Indigoid vat dyestufis of the general formula wherein R represents a benzene nucleus substituted by at least one alkoxy-alkoxy group.

5. The indigoid vat dyestufi of the formula JAROSLAV FROEHLICH. 

